Chemical vapor deposition process for depositing titanium nitride films from an organo-metallic compound

ABSTRACT

A process for depositing titanium nitride films containing less than 5% carbon impurities and less than 10% oxygen impurities by weight via chemical vapor deposition is disclosed. Sheet resistance of the deposited films is generally be within a range of about 1 to 10 ohms per square. The deposition process takes place in a deposition chamber that has been evacuated to less than atmospheric pressure and utilizes the organo-metallic compound tertiary-butyltris-dimethylamido-titanium and a nitrogen source as precursors. The deposition temperature, which is dependent on the nitrogen source, is within a range of 350° C. to 700° C. The low end of the temperature range utilizes nitrogen-containing gases such as diatomic nitrogen, ammonia, hydrazine, amides and amines which have been converted to a plasma. The higher end of the temperature range relies on thermal decomposition of the nitrogen source for the production of reaction-sustaining radicals. In such a case, the use of diatomic nitrogen gas is precluded because of its high dissociation temperature. Other materials may be simultaneously incorporated in the titanium nitride films during either embodiment of the deposition process as heretofore described. For example, a titanium nitride film incorporating aluminum and having the general formula TiAIN may be deposited by introducing aluminum-containing compounds. Additionally, a titanium nitride film incorporating tungsten and having the general formula TiNW may be deposited by introducing tungsten-containing compounds.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a continuation of application Ser. No.09/148,373, filed Sep. 4, 1998, pending, which is related to applicationSer. No. 09/148,371, titled CHEMICAL VAPOR DEPOSITION PROCESS FORDEPOSITING TITANIUM SILICIDE FILMS FROM AN ORGANO-METALLIC COMPOUND,which was filed on Sep. 4, 1998, now U.S. Pat. No. 6,168,837, issuedJan. 2, 2001.

BACKGROUND OF THE INVENTION

[0002] 1. Field of the Invention

[0003] This invention relates to integrated circuit fabricationtechnology and, more specifically, to processes for depositing titaniumnitride films via chemical vapor deposition.

[0004] 2. State of the Art

[0005] The compound titanium nitride (TiN) has numerous potentialapplications because it is extremely hard, chemically inert (although itreadily dissolves in hydrofluoric acid), an excellent conductor,possesses optical characteristics similar to those of gold, and has amelting point around 3000° C. This durable material has long been usedto gild inexpensive jewelry and other art objects. However, during thelast ten to twelve years, important uses have been found for TiN in thefield of integrated circuit manufacturing. Not only is TiN unaffected byintegrated circuit processing temperatures and most reagents, it alsofunctions as an excellent barrier against diffusion of dopants betweensemiconductor layers. In addition, TiN also makes excellent ohmiccontact with other conductive layers.

[0006] In a common application for integrated circuit manufacture, acontact opening is etched through an insulative layer down to adiffusion region to which electrical contact is to be made. Titaniummetal is then sputtered over the wafer so that the exposed surface ofthe diffusion region is coated. The titanium metal is eventuallyconverted to titanium silicide, thus providing an excellent conductiveinterface at the surface of the diffusion region. A titanium nitridebarrier layer is then deposited, coating the walls and floor of thecontact opening. Chemical vapor deposition of tungsten or polysiliconfollows. In the case of tungsten, the titanium nitride layer providesgreatly improved adhesion between the walls of the opening and thetungsten metal. In the case of the polysilicon, the titanium nitridelayer acts as a barrier against dopant diffusion from the polysiliconlayer into the diffusion region.

[0007] At least five processes are presently used for creating thintitanium nitride films: (1) reactive sputtering; (2) annealing of asputter-deposited titanium layer in a nitrogen ambient; (3) ahigh-temperature atmospheric pressure chemical vapor deposition (APCVD)process, using titanium tetrachloride, nitrogen and hydrogen asreactants; (4) a low-temperature APCVD process, using ammonia andtetrakis-dialkylamido-titanium compounds which have the generic formulaTi(NR₂)₄ as precursors; and (5) a low-pressure chemical vapor deposition(LPCVD) process, using tetrakis-dialkylamido-titanium compounds as thesole precursor. FIG. 1 depicts the structural formula oftetrakis-dialkylamido-titanium. Each of the “R” groups may be as simpleas a methy group (CH₃—) or they may be more complex alkyl groups. Eachof the processes enumerated above has its associated problems.

[0008] Both reactive sputtering and nitrogen ambient annealing ofdeposited titanium result in films having poor step coverage, which arenot useable in submicron processes. Chemical vapor deposition processeshave an important advantage in that conformal layers of any thicknessmay be deposited. This is especially advantageous inultra-large-scale-integration circuits, where minimum feature widths maybe smaller than 0.3 μm. Layers as thin as 10 Å may be readily producedusing CVD. However, TiN coatings prepared using the high-temperatureAPCVD process must be prepared at temperatures between 900-1000° C. Thehigh temperatures involved in this process are incompatible withconventional integrated circuit manufacturing processes. Hence,depositions using the APCVD process are restricted to refractorysubstrates such as tungsten carbide. The low-temperature APCVD, on theother hand, though performed within a temperature range of 100-400° C.that is compatible with conventional integrated circuit manufacturingprocesses, is problematic because the precursor compounds (ammonia andTi(NR₂)₄) react spontaneously in the gas phase. Consequently, specialprecursor delivery systems are required to keep the gases separatedduring delivery to the reaction chamber. In spite of special deliverysystems, the highly spontaneous reaction makes full wafer coveragedifficult to achieve. Even when achieved, the deposited films tend tolack uniform conformality, are generally characterized by poor stepcoverage, and tend to deposit on every surface within the reactionchamber, leading to particle problems. A problem with the LPCVD processis that the deposited TiN films are high in carbon content even if theprecursor is limited to tetrakis-dialkylamido-titanium, the compound ofthe group which contains the fewest carbon atoms. The carbon atomswithin the precursor molecules are incorporated into the film as theprecursor molecules dissociate. Although it is possible to reduce thecarbon content of the films by annealing them in ammonia and nitrogengases, the films attain neither the purity nor the conductivity ofsputtered films.

[0009] What is needed is a new chemical vapor deposition process whichwill provide highly conformal TiN films of high purity and with stepcoverage that is suitable for sub-0.25 μm generations of integratedcircuits.

BRIEF SUMMARY OF THE INVENTION

[0010] This invention includes various processes for depositing titaniumnitride films containing less than 5 percent carbon impurities and lessthan 10 percent oxygen impurities by weight via chemical vapordeposition and the use of a metal-organic precursor compound. Sheetresistance of the deposited films is within a range of about 1 to 10ohms per square. The deposition process takes place in a depositionchamber that has been evacuated to less than atmospheric pressure andutilizes the organo-metallic compoundtertiary-butyltris-dimethylamido-titanium (TBTDMAT) and a nitrogensource as precursors. The compoundtertiary-butyltris-dimethylamido-titanium has the formula(CH₃)₃CTi(N(CH₃)₂)₃. FIG. 2 depicts the structural formula oftertiary-butyltris-dimethylamido-titanium. It will be noted that onedimethylamido group of the tetrakis-dimethylamido-titanium molecule hasbeen replaced with a tertiary butyl group. The tertiary butyl group ismore easily removed from the molecule not only because it is larger thanthe dimethyl amido group, but because the carbon-titanium bond is weakerthan the nitrogen-titanium bonds. The resultant molecule is morereactive than tetrakis-dimethylamido-titanium and, in a chemical vapordeposition reaction, should produce films having a lower percentage ofcarbon impurities. The deposition temperature, which is dependent on thenitrogen source, is within a range of 350° C. to 700° C. The low end ofthe temperature range utilizes nitrogen-containing gases such asdiatomic nitrogen, ammonia, amides, amines and hydrazine which have beenconverted to a plasma. The higher end of the temperature range relies onthermal decomposition of the nitrogen source for the production ofreaction-sustaining radicals. In such a case, the use of diatomicnitrogen gas is precluded because of its high dissociation temperature.

[0011] Other materials may be incorporated in the titanium nitride filmsduring either embodiment of the deposition process as heretoforedescribed. For example, a titanium nitride film incorporating aluminumand having the general formula TiAIN may be deposited by introducingaluminum-containing compounds such as aluminum chloride (AlCl₃)dimethylethylamidoalane (DMEAA) or dimethylaluminumhydride (DMAH) alongwith the TBTDMAT and nitrogen-containing compounds. Additionally, atitanium nitride film incorporating tungsten and having the generalformula TiNW may be deposited by introducing tungsten halide compoundssuch as WF₆ or WCl₆ or an organo-metallic compound such asbis(2,4-dimethylpentadienyl)tungsten along with the TBTDMAT andsilicon-containing compounds. The aluminum-containing compounds ortungsten-containing compounds may be introduced in a manner similar tothat of the other reactants using the temperature guidelines heretoforeprovided for each embodiment of the invention.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

[0012] In the drawings, which illustrate what is currently considered tobe the best mode for carrying out the invention:

[0013]FIG. 1 is a structural diagram of tetrakis-dialkylamido-titanium;

[0014]FIG. 2 is a structural diagram oftertiary-butyltris-dialkylamido-titanium; and

[0015]FIG. 3 is a block schematic diagram of a low-pressure chemicalvapor deposition reactor system.

DETAILED DESCRIPTION OF THE INVENTION

[0016] A new low-pressure chemical vapor deposition process fordepositing highly conformal titanium nitride films having carbonimpurities of less than 5% by weight and oxygen impurities of less than10% by weight and having sheet resistance values within a range of about1 to 10 ohms per square will be described in reference to thelow-pressure chemical vapor deposition reactor system depicted in FIG.3.

[0017] A first embodiment of the invention which utilizes a cold-wallplasma enhanced chemical vapor deposition (PECVD) process will bedescribed with reference to FIG. 3. Although the following descriptionof the process represents what the inventor believes is the preferredembodiment of the process, the process may be practiced in eithercold-wall or hot-wall plasma-enhanced chemical vapor depositionchambers, with or without premixing of the reactants. Furthermore,although the invention is directed to a technique for depositingconformal titanium nitride layers for use in the manufacture ofintegrated circuits, the process is also applicable to the deposition oftitanium nitride on substrates other than semiconductor wafers.

[0018] Referring now to FIG. 3, atertiary-butyltris-dimethylamido-titanium metal-organic source gas isproduced by heating liquid tertiary-butyltrisdimethylamido-titanium (themetal-organic precursor compound). The gas phase metal-organic compoundtransported by a carrier gas is admitted into a pre-mixing chamber 3through control valve 1 and a nitrogen-containing gas such as N₂, NH₃, ahydrazine, an amide or an amine (or some combination thereof) isadmitted into the pre-mixing chamber 3 through control valve 2. Use of acarrier gas may also be desired for the transport of certain amides oramines. The carrier gases employed may be H₂, N₂, He or Ar. In the casewhere N₂ is utilized as a carrier gas for the metal-organic compound, noother nitrogen-containing gas is required. Following the pre-mixing ofthe gas phase metal-organic compound and the nitrogen-containingcompound in pre-mixing chamber 3, the pre-mixed gases are admitted tothe deposition chamber 4. Optionally, the gas-phase metal-organiccompound may be mixed with an inert carrier gas by bubbling the carriergas through the heated metal-organic compound. As a further option, theliquid metal-organic compound may be converted to a fine spray or mistby a liquid injector (not shown). The mist is then passed through avaporizer chamber (also not shown) en route to the deposition chamber.Within the deposition chamber 4, a semiconductor wafer 5 is heated to atemperature within a range of about 350° C. to 500° C. by convectionfrom substrate holder 6 (such as a graphite or alumina boat) that, inturn, is heated via halogen lamps 7. The walls of the chamber aremaintained at a temperature which is sufficiently high to preventcondensation of TBTDMAT molecules thereon, yet not so high thatdecomposition of TBTDMAT molecules will occur. In a cold-wall reactor,the wafer is maintained at a temperature that is considerably higherthan that of the chamber walls, thereby minimizing deposition oftitanium nitride on the chamber walls. As a general rule, the chamberwalls should be maintained within a range of about 50° C. to 400° C.,and optimally within a range of about 100° C. to 200° C.

[0019] Still referring to FIG. 3, the pre-mixed combination ofmetal-organic compound, one or more carrier gases and molecules of anitrogen-containing gas such as N₂, NH₃, hydrazine, amides and aminesenter deposition chamber 4 through shower head 15. A radio-frequency(RF) voltage, supplied by radio-frequency generator 8, is appliedbetween substrate holder 6 and deposition chamber wall 16, thus forminga plasma in which some of the metal-organic molecules andnitrogen-containing molecules are converted to radicals, ions, andmetastables. An RF power density of about 1 to 2 watts/cm² is applied tothe wafer in order to generate the plasma. Other remote plasmageneration systems, such as a microwave plasma generator, can also beused with comparable results. Metal-organic compound molecules areadsorbed on the surface of the wafer 5, and nitrogen-containing radicalsreact with the adsorbed metal-organic molecules to form a uniformlythick titanium nitride layer on the surface of the wafer.

[0020] As an alternative to the procedure employed above for the firstembodiment of the process, a remote source PECVD reactor may be employedwith similar results. In such a case, only the nitrogen-containing gasneed be passed through the plasma generator; the metal-organic compoundmay bypass the plasma generator en route to the deposition chamber 4.

[0021] Although the desired reaction may be effected at a pressurewithin a range of about 0.1 torr to 100 torr, a preferred range isdeemed to be about 0.2 torr to 10 torr. A constant deposition pressurewithin that preferred range is monitored and maintained by conventionalpressure control components consisting of pressure sensor 9, pressureswitch 10, air operating vacuum valve 11 and pressure control valve 12.The byproducts of the reaction and the carrier gases (if carrier gasesare used) pass through particulate filter 13 and escape through exhaustvent 14 with the aid of a blower 17 to complete the process.

[0022] The deposited titanium nitride films can be annealed in anitrogen-containing ambiance at temperatures within a range of 400° C.to 700° C. Additionally, the deposited films can be annealed in a plasmaenvironment, which typically reduces carbon and oxygen impurities in thefilms, thereby decreasing resistivity of the films by as much as 50percent.

[0023] A second embodiment of the invention will also be described withreference to the diagrammatic representation of the chemical vapordeposition chamber of FIG. 3. However, for this embodiment, no RF poweris applied between the substrate holder 6 and the chamber wall 16.Instead, increased wafer temperature is relied on to effect a reactionbetween the tertiary-butyltris-dimethylamido-titanium and thenitrogen-containing gas. Diatomic nitrogen gas, because its dissociationtemperature is greater than temperatures compatible with semiconductorprocessing, is not used for the second embodiment of the process. Exceptfor the use of higher temperatures within a range of about 500° C. to700° C. and the lack of a plasma-generating RF power, other features ofthe process remain the same.

[0024] Other materials may be simultaneously incorporated in thetitanium nitride films during either embodiment of the depositionprocess as heretofore described. For example, a titanium nitride filmincorporating aluminum and having the general formula TiAIN may bedeposited by introducing aluminum-containing compounds such as aluminumchloride (AlCl₃) dimethylethylamidoalane (DMEAA) ordimethylaluminumhydride (DMAH) along with the TBTDMAT andnitrogen-containing compounds. The aluminum-containing compound may beintroduced in a manner similar to that of the other reactants using thetemperature guidelines heretofore provided for each embodiment of theinvention. Additionally, a titanium nitride film incorporating tungstenand having the general formula TiWN may be deposited by introducingorgano-metallic compounds such as bis(2,4-dimethylpentadienyl)tungstenor tungsten halide compounds such as WF₆ or WCI₆ along with the TBTDMATand silicon-containing compounds. The aluminum-containing compounds orthe tungsten-containing compounds may be introduced in a manner similarto that of the other reactants using the temperature guidelinesheretofore provided for each embodiment of the invention.

[0025] While several embodiments of the process for depositing titaniumnitride using tertiary-butyltris-dimethylamido-titanium as a precursorcompound have been disclosed herein, it will be obvious to those havingordinary skill in the art that modifications and changes may be madethereto without affecting the scope and spirit of the invention asclaimed.

What is claimed is:
 1. A method for forming a predominantly titaniumnitride film comprising: placing a substrate in a chemical vapordeposition chamber to be maintained at a sub-atmospheric pressure level;premixing a tertiary-butyltris-dimethylamido-titanium compound and anitrogen-containing gas in a premixing chamber; admitting the premixedgas-phase tertiary-butyltris-dimethylamido-titanium compound andnitrogen-containing gas into said chemical vapor deposition chamber;applying a plasma generation system for for forming a plasma comprisingsaid tertiary-butyltris-dimethylamido-titanium compound and saidnitrogen-containing gas; heating said substrate to a temperature rangingfrom about 350° C. to about 700° C.; and forming said predominantlytitanium nitride film having less than about 5% carbon impurities byweight and a sheet resistance of approximately 1 to 10 ohms per squareon a portion of said substrate.
 2. The method of claim 1, wherein saidplacing the substrate within a chemical vapor deposition chambermaintained at a sub-atmospheric pressure comprises placing asemiconductor material selected from the group consisting of silicon,germanium, and gallium arsenide.
 3. The method of claim 1, wherein saidadmitting nitrogen-containing gas into said chemical vapor depositionchamber comprises admitting a nitrogen-containing gas selected from thegroup consisting of ammonia, amides, amines, and hydrazine into saidchemical vapor deposition chamber.
 4. The method of claim 1, furthercomprising transporting said gas-phasetertiary-butyltris-dimethylamido-titanium compound to said chemicalvapor deposition chamber including a carrier gas.
 5. The method of claim4, wherein said transporting gas-phasetertiary-butyltris-dimethylamido-titanium to said chemical vapordeposition chamber using a carrier gas comprises transporting saidgas-phase tertiary-butyltris-dimethylamido-titanium to said chemicalvapor deposition chamber including a carrier gas selected from the groupconsisting of N₂, H₂, He and Ar.
 6. The method of claim 1, furthercomprising transporting said nitrogen-containing gas to said chemicalvapor deposition chamber including a carrier gas.
 7. The method of claim1, wherein said forming a predominantly titanium nitride film havingless than about 5% carbon impurities by weight and a sheet resistance ofapproximately 1 to 10 ohms per square further comprises forming thepredominantly titanium nitride film comprising less than 10% oxygenimpurities by weight.
 8. The method of claim 1, wherein said placing thesubstrate within a chemical vapor deposition chamber maintained atsub-atmospheric pressure comprises placing a semiconductor wafer withina chemical vapor deposition chamber maintained at sub-atmosphericpressure.
 9. The method of claim 1, further comprising admitting analuminum-containing compound into said chemical vapor deposition chamberin combination with said gas-phase tertiarybutyltris-dimethylamido-titanium compound and said nitrogen-containinggas to include aluminum into said predominantly titanium nitride filmhaving less than about 5% carbon impurities by weight.
 10. The method ofclaim 9, wherein said admitting an aluminum-containing compound intosaid chemical vapor deposition chamber in combination with saidgas-phase tertiary butyltris-dimethylamido-titanium and saidnitrogen-containing gas comprises admitting AlCl₃ into said chemicalvapor deposition chamber.
 11. The method of claim 9, wherein saidadmitting an aluminum-containing compound into said chemical vapordeposition chamber in combination with said gas-phase tertiarybutyltris-dimethylamido-titanium compound and said nitrogen-containinggas comprises admitting dimethylethylamidoalane into said chemical vapordeposition chamber.
 12. The method of claim 9, wherein said admitting analuminum-containing compound into said chemical vapor deposition chamberin combination with said gas-phase tertiarybutyltris-dimethylamido-titanium compound and said nitrogen-containinggas comprises admitting dimethylaluminumhydride into said chemical vapordeposition chamber.
 13. The method of claim 1, further comprisingadmitting a tungsten-containing compound into said chemical vapordeposition chamber in combination with said gas-phasetertiary-butyltris-dimethylamido-titanium compound and saidnitrogen-containing for including tungsten into said predominantlytitanium nitride film having less than about 5% carbon impurities byweight.
 14. The method of claim 13, wherein said admitting atungsten-containing compound into said chemical vapor deposition chamberin combination with said gas-phasetertiary-butyltris-dimethylamido-titanium compound and saidnitrogen-containing gas comprises admittingbis(2,4-dimethylpetadienyl)tungsten into said chemical vapor depositionchamber.
 15. The method of claim 13, wherein said admitting atungsten-containing compound into said chemical vapor deposition chamberin combination with said gas-phasetertiary-butyltris-dimethylamido-titanium and said nitrogen-containinggas comprises admitting a tungsten halide compound selected from thegroup consisting of WF₆ and WCl₆ into said chemical vapor depositionchamber.
 16. The method of claim 1, further comprising annealing saidpredominantly titanium nitride film having less than about 5% carbonimpurities by weight and a sheet resistance of approximately 1 to 10ohms per square in a nitrogen ambiance.
 17. A method for forming apredominantly titanium nitride film on a substrate comprising: placingthe substrate within a plasma-enhanced chemical vapor deposition (PECVD)chamber; establishing a sub-atmospheric pressure in said PECVD chamber;admitting gas-phase tertiary-butyltris-dimethylamido-titanium into saidPECVD chamber; admitting nitrogen-containing gas into said PECVDchamber; heating said substrate to a temperature within a range of about350° C. to 700° C.; generating a plasma in said PECVD chamber in thepresence of said tertiary-butyltris-dimethylamido-titanium and saidnitrogen-containing gas; and depositing said predominantly titaniumnitride film on a portion of said substrate, said predominantly titaniumnitride film having an as deposited sheet resistance of approximately 1to 10 ohms per square.
 18. The method of claim 17, wherein saidadmitting nitrogen-containing gas into said PECVD chamber comprisesadmitting a nitrogen-containing gas selected from the group consistingof diatomic nitrogen, ammonia, amides and amines.
 19. The method ofclaim 17, wherein said depositing said predominantly titanium nitridefilm on said substrate comprises depositing a titanium nitride filmcontaining less than 5% carbon impurities by weight and less than 10%oxygen impurities by weight.
 20. The method of claim 17, furthercomprising admitting an aluminum-containing compound into said PECVDchamber in combination with said gas-phasetertiary-butyltris-dimethylamido-titanium and said nitrogen-containinggas.
 21. The method of claim 20, wherein said admitting analuminum-containing compound into said PECVD chamber in combination withsaid gas-phase tertiary-butyltris-dimethylamido-titanium and saidnitrogen-containing gas comprises admitting AlCl₃ into said PECVDchamber.
 22. The method of claim 20, wherein said admitting analuminum-containing compound into said PECVD chamber in combination withsaid gas-phase tertiary-butyltris-dimethylamido-titanium and saidnitrogen-containing gas comprises admitting dimethylethylamidealane intosaid PECVD chamber.
 23. The method of claim 20, wherein said admittingan aluminum-containing compound into said PECVD chamber in combinationwith said gas-phase tertiary-butyltris-dimethylamido-titanium and saidnitrogen-containing gas comprises admitting dimethylaluminumhydride intosaid PECVD chamber.
 24. The method process of claim 17, furthercomprising admitting a tungsten-containing compound into said PECVDchamber in combination with said gas-phasetertiary-butyltris-dimethylamido-titanium and said nitrogen-containinggas, thereby incorporating tungsten into said predominantly titaniumnitride film.
 25. The method of claim 24, wherein said admitting atungsten-containing compound into said PECVD chamber in combination withsaid gas-phase tertiary-butyltris-dimethylamido-titanium and saidnitrogen-containing gas comprises admittingbis(2,4-dimethylpetadienyl)tungsten into said PECVD chamber.
 26. Themethod of claim 24, wherein said admitting a tungsten-containingcompound into said PECVD chamber in combination with said gas-phasetertiary-butyltris-dimethylamido-titanium and said nitrogen-containinggas comprises admitting a tungsten halide compound selected from thegroup consisting of WF₆ and WCl₆ into said PECVD chamber.
 27. The methodof claim 1, wherein said remote plasma generation system comprises aradio-frequency generator.
 28. The process of claim 1, wherein saidremote plasma generation system comprises a microwave plasma generator.